CN101207189A - Anode and preparation method thereof as well as lithium ion secondary battery - Google Patents
Anode and preparation method thereof as well as lithium ion secondary battery Download PDFInfo
- Publication number
- CN101207189A CN101207189A CNA2006101676750A CN200610167675A CN101207189A CN 101207189 A CN101207189 A CN 101207189A CN A2006101676750 A CNA2006101676750 A CN A2006101676750A CN 200610167675 A CN200610167675 A CN 200610167675A CN 101207189 A CN101207189 A CN 101207189A
- Authority
- CN
- China
- Prior art keywords
- adhesive
- positive electrode
- graphite
- carbon fiber
- conductive agent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to a positive electrode of a battery, which comprises a current collector and positive electrode material coated on the current collector. The positive electrode material comprises positive electrode active material, conductive agent and binding agent, the binding agent includes hydrophilic binding agent; wherein, the conductive agent comprises graphite and carbon fiber, and the weight ratio of the graphite and the carbon fiber is 100: 1 to 100: 10. The graphite and the carbon fiber are mixed as the conductive agent according to the weight ratio of 100: 1 to 100: 10, aqueous dispersant and the binding agent including hydrophilic binding agent are chosen to prepare the positive electrode of the battery, thus the finished product rate of the positive electrode of the battery is high, and the electrical conductivity is good.
Description
Technical field
The invention relates to a kind of positive pole and preparation method thereof and comprise the battery that this is anodal, specifically, the invention relates to a kind of positive pole and preparation method thereof and comprise the lithium rechargeable battery that this is anodal.
Background technology
Lithium rechargeable battery refers to respectively the ion battery that constitutes as both positive and negative polarity with two compounds that can reversibly embed with the removal lithium embedded ion.Because of its specific energy height, operating voltage height, operating temperature range is wide, self-discharge rate is low, have extended cycle life, pollution-free, in light weight, advantage such as security performance is good, thereby application is extensive.
Lithium rechargeable battery generally includes battery container and is sealed in this battery container interior electrode group and electrolyte; Described electrode group comprises positive pole, negative pole and the barrier film between positive pole and negative pole; Described positive pole comprises plus plate current-collecting body and applies positive electrode on it; Described positive electrode comprises positive active material, conductive agent and adhesive.Described positive pole comprises collector and applies positive electrode on it; Described positive electrode comprises positive active material, conductive agent and adhesive.During anode, generally positive electrode and dispersant are made the slurry that contains positive electrode in preparation, be coated to collection liquid surface, the dispersant in the slurry can be removed in the step of subsequent preparation battery (as drying etc.).
Organic dispersing agent commonly used in the lithium ion secondary battery positive electrode preparation process is N-methyl pyrrolidone (NMP), N, dinethylformamide (DMF), N, one or more in N-diethylformamide (DEF), methyl-sulfoxide (DMSO) and the oxolane (THF).Because these organic dispersing agents can cause the severe contamination to environment, therefore the angle from environmental protection is more prone to select for use for example aqueous dispersions such as the aqueous solution replacement organic dispersing agent of water, ethanol or ethanol.When using organic dispersing agent, the adhesive in the positive electrode is mainly based on hydrophobic adhesive; And when selecting aqueous dispersion for use, need to improve the ratio of hydrophilic adhesive in the adhesive, even replace hydrophobic adhesive fully with hydrophilic adhesive, just more help adhesive is evenly disperseed.But when selecting for use aqueous dispersion to prepare anode with the adhesive that contains hydrophilic adhesive, the slurry that contains positive electrode is after being coated to collection liquid surface, conductive agent of using always in the positive electrode such as acetylene black, carbon black can be reunited, cause conductive agent skewness on collector, positive electrode combines not tight with collector, the anodal surface irregularity that the result makes, the phenomenon that occurs " falling piece " easily, the positive electrode that is conductive agent reunion position comes off from collector, therefore causes the low problem of anodal rate of finished products.
In sum, the prior art positive pole that contains hydrophilic adhesive exists because conductive agent skewness and the low problem of rate of finished products.
Summary of the invention
The objective of the invention is to overcome that positive pole that prior art contains hydrophilic adhesive exists because conductive agent skewness and the low shortcoming of rate of finished products, a kind of conductive agent high positive pole of rate of finished products that is evenly distributed is provided.
Second purpose of the present invention provides the preparation method of above-mentioned positive pole.
The 3rd purpose of the present invention provides the lithium rechargeable battery that uses above-mentioned positive pole.
The present inventor notices, when selecting for use aqueous dispersion to prepare anode with the adhesive that contains hydrophilic adhesive, the slurry that contains positive electrode is after being coated to collection liquid surface, conductive agent of using always in the positive electrode such as acetylene black, carbon black can be reunited, cause conductive agent skewness on collector, positive electrode combines not tight with collector, the anodal surface irregularity that the result makes, the phenomenon that occurs " falling piece " easily, the positive electrode that is conductive agent reunion position comes off from collector, therefore causes the low problem of anodal rate of finished products.The present inventor finds unexpectedly, graphite and carbon fiber are mixed when preparing anode as conductive agent and the adhesive selecting aqueous dispersion for use and contain hydrophilic adhesive according to 100: 1 to 100: 10 weight ratio, conductive agent just can distribute very evenly, the phenomenon that " falling piece " also do not occur has improved the rate of finished products of anode greatly.
The invention provides a kind of anode, this positive pole comprises collector and the positive electrode that is coated on this collector; Described positive electrode comprises positive active material, conductive agent and adhesive, and described adhesive contains hydrophilic adhesive, and wherein, described conductive agent comprises graphite and carbon fiber, and the weight ratio of described graphite and carbon fiber is 100: 1 to 100: 10.
The invention provides the preparation method of above-mentioned anode, this method comprises that the slurry that will contain positive electrode is coated on the collector, dry, calendering, described positive electrode comprises positive active material, conductive agent and adhesive, and described adhesive contains hydrophilic adhesive, wherein, described conductive agent comprises graphite and carbon fiber, and the weight ratio of described graphite and carbon fiber is 100: 1 to 100: 10.
The present invention also provides a kind of lithium rechargeable battery, and this battery comprises battery container and is sealed in this battery container interior electrode group and electrolyte; Described electrode group comprises positive pole, negative pole and the barrier film between positive pole and negative pole, wherein, and described positive pole just very of the present invention.
The present invention is with graphite and carbon fiber mixes as conductive agent according to 100: 1 to 100: 10 weight ratio and select for use aqueous dispersion and the adhesive that contains hydrophilic adhesive to prepare anode, gained anode rate of finished products height and good conductivity.As the positive pole of embodiment 1 select for use weight ratio be 100: 3 graphite and carbon fiber as conductive agent, anodal rate of finished products can reach 100%; And Comparative Examples 1 only with acetylene black as conductive agent, Comparative Examples 2 only with carbon fiber as conductive agent because the conductive agent agglomeration is serious, Comparative Examples 1 anodal rate of finished products only is 65%, Comparative Examples 2 anodal rate of finished productss only are 95%.
Embodiment
The anode that the invention provides comprises collector and the positive electrode that is coated on this collector; Described positive electrode comprises positive active material, conductive agent and adhesive, and described adhesive contains hydrophilic adhesive, and wherein, described conductive agent comprises graphite and carbon fiber, and the weight ratio of described graphite and carbon fiber is 100: 1 to 100: 10.
Conductive agent is used to increase the conductivity of electrode, reduce the internal resistance of battery, but be to use conductive agent commonly used such as acetylene black, carbon black and select aqueous dispersion for use and contain the adhesive of hydrophilic adhesive, when the preparation electrode, " falling piece " phenomenon can take place all, cause the rate of finished products of battery low.Of the present invention anodal adopt weight ratio be 100: 1 to 100: 10 graphite and carbon fiber as conductive agent, not only improved anodal conductivity, and when the preparation electrode, agglomeration can not take place, anodal rate of finished products is improved.The weight ratio of preferred described graphite and carbon fiber is 100: 2 to 100: 5.
This area can may be used to the present invention as the graphite of lithium ion secondary battery positive electrode conductive agent, reaches goal of the invention of the present invention.Described graphite can be divided into native graphite and Delanium.Native graphite comprises types such as amorphous graphite and flaky graphite, Delanium then be with some easy graphited material with carbon element such as coke, pitch plasma carry out pulverizing after the graphitization, screening and the material that forms.General by median particle diameter D
50The particle size distribution situation that reflects graphite.Described herein median particle diameter D
50Be by being particle diameter with transverse axis a, longitudinal axis b is that the particle size distribution of the volume reference represented of the a-b coordinate system of population is tried to achieve.In above-mentioned particle size distribution, begin the accumulative total volume from the little particle diameter of a value, a value that the accumulative total volume reaches 50% o'clock correspondence of integral body is median particle diameter D
50The median particle diameter D of preferred described graphite
50Value is 4-50 micron, more preferably D
50Value is the 4-30 micron.In addition, this area is generally by 002 interplanar distance that records with powder X-ray diffractometry and the specific area reflection degree of graphitization that graphite reached as conductive agent, 002 interplanar distance that the present invention preferably records with powder X-ray diffractometry is the 0.3354-0.3660 nanometer, specific area is the graphite of 0.5-8 meters squared per gram, more preferably 002 interplanar distance is the 0.3354-0.3380 nanometer, and specific area is the graphite of 0.5-6 meters squared per gram.
This area can may be used to the present invention as the carbon fiber of lithium ion secondary battery positive electrode conductive agent, reaches goal of the invention of the present invention.Known in this field, described carbon fiber is to be fiber more than 90% by the phosphorus content that polyacrylonitrile fibre, pitch fibers or viscose glue dimension etc. make through carbonisation.The length of preferred described carbon fiber is the 10-100 micron, and diameter is the 100-2000 nanometer, and more preferably the length of described carbon fiber is the 20-40 micron, and diameter is the 1000-2000 nanometer.
Improve because the present invention only relates to the conductive agent proportioning that prior art is contained the lithium ion secondary battery positive electrode of hydrophilic adhesive, therefore other The Nomenclature Composition and Structure of Complexes to lithium ion secondary battery positive electrode has no particular limits.
For example, positive electrode of the present invention is a benchmark with described positive electrode, and the content of described conductive agent is 0.5-15 weight %, and the content of described adhesive is 0.01-8 weight %, and the content of described positive active material is 77-99 weight %; Be benchmark with described positive electrode preferably, the content of described conductive agent is 1-6 weight %, and the content of described adhesive is 1-5 weight %, and the content of described positive active material is 90-95 weight %.
Positive pole of the present invention has no particular limits hydrophilic adhesive and hydrophobic adhesive, can adopt known in the art all can be used for the hydrophilic adhesive and the hydrophobic adhesive of lithium rechargeable battery.The present invention is not only applicable to contain the positive pole of hydrophilic adhesive, also can be used for only containing the positive pole of hydrophobic adhesive, therefore, the present invention has no particular limits the ratio of described hydrophobic adhesive and hydrophilic adhesive, contain hydrophilic adhesive and hydrophobic adhesive for the preferred described adhesive of the needs of environmental protection, with the adhesive is benchmark, and the content of described hydrophilic adhesive is 50-100 weight %, and the content of preferred hydrophilic adhesive is 90-100 weight %.Described adhesive can use with the aqueous solution or emulsion form, also can use with solid form, preferably use with the aqueous solution or emulsion form, have no particular limits the concentration of described hydrophilic adhesive solution and the concentration of described hydrophobic adhesive emulsion this moment, the viscosity that can be coated with according to the slurry of positive pole that will prepare and cathode size and the requirement of operability are adjusted flexibly to this concentration, the concentration of for example described hydrophilic adhesive solution can be 0.5-4 weight %, and the concentration of described hydrophobic adhesive emulsion can be 10-80 weight %.Described hydrophilic adhesive can be selected from one or more in hydroxypropyl methylcellulose, carboxymethyl cellulose, hydroxyethylcellulose and the polyvinyl alcohol; Described hydrophobic adhesive can be selected from polytetrafluoroethylene and/or butadiene-styrene rubber.
Described positive active material can be a various positive active material known in those skilled in the art, can be selected from for example Li
xNi
1-yCoO
2(wherein, 0.9≤x≤1.1,0≤y≤1.0), Li
mMn
2-nB
nO
2(wherein, B is a transition metal, 0.9≤m≤1.1,0≤n≤1.0) and Li
1+aM
bMn
2-bO
4In (wherein ,-0.1≤a≤0.2,0≤b≤1.0, M is one or more in lithium, boron, magnesium, aluminium, titanium, chromium, iron, cobalt, nickel, copper, zinc, gallium, yttrium, fluorine, iodine, the element sulphur) one or more.Preferred described positive active material is selected from one or more in lithium cobalt oxygen, lithium nickel oxygen, lithium manganese oxygen, lithium-nickel-cobalt-oxygen, Li-Ni-Mn-O, lithium cobalt manganese oxygen and the Li-Ni-Mn-Co-O.
Described collector can be a various collector known in those skilled in the art, and as aluminium foil, Copper Foil, nickel plated steel strip etc., the present invention selects for use aluminium foil to make collector.
Anode preparation method provided by the invention comprises that the slurry that will contain positive electrode is coated on the collector, dry, calendering, described positive electrode comprises positive active material, conductive agent and adhesive, described adhesive contains hydrophilic adhesive, wherein, described conductive agent comprises graphite and carbon fiber, and the weight ratio of described graphite and carbon fiber is 100: 1 to 100: 10.
Prepare positive pole of the present invention, with weight ratio be 100: 1 to 100: 10 graphite and carbon fiber as conductive agent, the weight ratio of preferred described graphite and carbon fiber is 100: 2 to 100: 5.Described graphite can be selected from the various graphite of this area as conductive agent, the median particle diameter D of preferred described graphite
50Value is the 4-50 micron, and 002 interplanar distance that records with powder X-ray diffractometry is the 0.3354-0.3660 nanometer, and specific area is the 0.5-8 meters squared per gram, more preferably the median particle diameter D of described graphite
50Value is the 4-30 micron, and 002 interplanar distance that records with powder X-ray diffractometry is the 0.3354-0.3380 nanometer, and specific area is the 0.5-6 meters squared per gram.Described carbon fiber can be selected from the various carbon fibers of this area as conductive agent, and the length of preferred described carbon fiber is the 10-100 micron, and diameter is the 100-2000 nanometer, and more preferably the length of described carbon fiber is the 20-40 micron, and diameter is the 1000-2000 nanometer.
The described slurry that contains positive electrode comprises positive electrode and dispersant, and the described slurry that contains positive electrode can blended anode material and dispersant preparation.Described dispersant can be water and/or hydrophilic alcohols, and preferred described dispersant is water and/or ethanol.In general, the consumption of dispersant can be coated on the described collector described slurry to get final product.With the described slurry that contains positive electrode is benchmark, and the content of described dispersant is 10-60 weight %, is preferably 15-50 weight %.The known coated weight that can control described slurry by the thickness of control coating slurry of those skilled in the art; Dispersant in the slurry can be removed in follow-up battery step (as drying etc.).
Described drying, the step of calendering, the same with prior art, promptly described drying usually under vacuum condition at 50-160 ℃, carry out under preferred 80-150 ℃.Described calendering can be adopted this area rolling condition commonly used, such as the 0.5-3.0 MPa.Described cut-parts are as well known to those skilled in the art, after calendering is finished, cut according to the anodal size of prepared battery request, obtain positive pole.
Lithium rechargeable battery provided by the invention comprises battery container and is sealed in this battery container interior electrode group and electrolyte; Described electrode group comprises positive pole, negative pole and the barrier film between positive pole and negative pole, wherein, and described positive pole just very of the present invention.Because the present invention only relates to the improvement to the prior art lithium ion secondary battery positive electrode, therefore other The Nomenclature Composition and Structure of Complexes to lithium rechargeable battery has no particular limits.
For example, consisting of of negative pole is conventionally known to one of skill in the art, and in general, negative pole comprises conducting base and coating and/or is filled in negative material on the conducting base.Described conducting base is conventionally known to one of skill in the art, for example can be selected from aluminium foil, Copper Foil, nickel plated steel strip, the Punching steel strip one or more.Described negative active core-shell material is conventionally known to one of skill in the art, it comprises negative electrode active material and adhesive, described negative electrode active material can be selected from the negative electrode active material of lithium rechargeable battery routine, as in native graphite, Delanium, petroleum coke, organic cracking carbon, carbonaceous mesophase spherules, carbon fiber, ashbury metal, the silicon alloy one or more.Described adhesive can be selected from the adhesive of lithium rechargeable battery routine, as in polyvinyl alcohol, polytetrafluoroethylene, CMC (CMC), the butadiene-styrene rubber (SBR) one or more.In general, the content of described adhesive is the 0.5-8 weight % of negative electrode active material, is preferably 2-5 weight %.
The solvent that is used to prepare cathode size of the present invention can be selected from conventional solvent, as being selected from N-methyl pyrrolidone (NMP), N, dinethylformamide (DMF), N, one or more in N-diethylformamide (DEF), methyl-sulfoxide (DMSO), oxolane (THF) and water and the alcohols.The consumption of solvent can be coated on the described collector described slurry and gets final product.In general, the consumption of solvent is that to make the concentration of electrode active material in the slurry be 40-90 weight %, is preferably 50-85 weight %.
Described barrier film has electrical insulation capability and liquid retainability energy, is arranged between positive pole and the negative pole, and is sealed in the battery case with positive pole, negative pole and electrolyte.Described barrier film can be the general various barrier films in this area, such as by those skilled in the art in the modified poly ethylene felt of respectively producing the trade mark, modified polypropene felt, ultra-fine fibre glass felt, vinylon felt or the nylon felt of known each manufacturer production and wettability microporous polyolefin film through welding or the bonding composite membrane that forms.
Described electrolyte is this area electrolyte commonly used, as the mixed solution of electrolyte lithium salt and nonaqueous solvents.Electrolyte lithium salt is selected from lithium hexafluoro phosphate (LiPF
6), in lithium perchlorate, LiBF4, hexafluoroarsenate lithium, lithium halide, chlorine lithium aluminate and the fluorocarbon based sulfonic acid lithium one or more.Organic solvent can be selected from chain acid esters and ring-type acid esters mixed solution, wherein the chain acid esters can be fluorine-containing for dimethyl carbonate (DMC), diethyl carbonate (DEC), methyl ethyl carbonate (EMC), carbonic acid first propyl ester (MPC), dipropyl carbonate (DPC) and other, sulfur-bearing or contain at least a in the chain organosilane ester of unsaturated bond.The ring-type acid esters can (γ-BL), sultone and other be fluorine-containing, sulfur-bearing or contain at least a in the ring-type organosilane ester of unsaturated bond for ethylene carbonate (EC), propene carbonate (PC), vinylene carbonate (VC), gamma-butyrolacton.In the described electrolyte, the concentration of electrolyte lithium salt is generally the 0.1-2 mol, is preferably the 0.8-1.2 mol.
Unless stated otherwise, all kinds of solvents of the present invention and reagent are commercially available analytical reagent.
The present invention is described further below in conjunction with embodiment.
Embodiment 1
Present embodiment illustrates positive pole provided by the invention and preparation method thereof and comprises the lithium rechargeable battery that this is anodal.
(1) Zheng Ji preparation
30 gram polytetrafluoroethylene are dissolved in about 500 grams make binder solution in the water, 940 gram Li-Ni-Mn-Co-Os (Ningbo JinHe New Materials Co., Ltd) join in the above-mentioned solution with graphite and the carbon fiber that 30 grams serve as conductive agent then, fully mix and make anode sizing agent, the mass ratio of described graphite and carbon fiber is 100: 5, the median particle diameter D of described graphite
50Value is 40 microns, and 002 interplanar distance that records with powder art X-ray diffraction method is 0.3357 nanometer, and specific area is 4 meters squared per gram; The length of described carbon fiber is 30 microns, and diameter is 500 nanometers; With tensile pulp machine this anode sizing agent is coated to thick 18 microns aluminium foil two sides equably.Through 125 ℃ of vacuum and heating dryings 1 hour, calendaring molding under 2.0 MPa pressure, cut-parts make the positive pole of millimeter (wide) * 130,360 millimeters (length) * 43.5 micron (thick), contain the positive active materials of 5.42 grams on every positive pole.Present embodiment makes 120 of anodes altogether, defective just very 0 of " falling piece " phenomenon wherein occurs, and anodal rate of finished products is 100%.
(2) preparation of negative pole
(Kynoar (PVDF) that serves as adhesive with 40 grams fully mixes electrically conductive graphite for soddif commodity, DAG22) powder 960 grams, is dissolved into about 500 grams and serves as in the N-methyl pyrrolidone of solvent, fully mixes and makes cathode size.With tensile pulp machine this cathode size is coated to the two sides that thickness is 10 microns the Copper Foil that serves as collector equably, makes that the coat side density of negative material is 9.5 milligrams/square centimeter.Through 125 ℃ of vacuum and heating dryings 1 hour, two rod milling train rolling formations.Cut-parts make the negative pole of millimeter (wide) * 130,330 millimeters (length) * 44.5 micron (thick), contain 2.25 graphite that restrain on the every negative pole.
(3) assembling of battery
To include in after positive pole, barrier film, negative pole lamination successively and the winding in 4.2 millimeters * 30 millimeters * 48 millimeters the square aluminum hull.
To contain 1 mole lithium hexafluoro phosphate (LiPF
6) ethylene carbonate: the Methylethyl carbonic ester: diethyl carbonate (EC/EMC/DEC) volume ratio be 1: 1: 1 electrolyte about 2.6 the gram, inject above-mentioned battery.The sealed cell aluminum hull can obtain lithium rechargeable battery of the present invention.
Comparative Examples 1
This Comparative Examples illustrates positive pole of prior art and preparation method thereof and comprises the lithium rechargeable battery that this is anodal.
Method according to embodiment 1 prepares positive pole and comprises the battery that this is anodal, and different is that the conductive agent of selecting for use is existing acetylene black commonly used.This Comparative Examples makes 134 of anodes altogether, defective just very 47 of " falling piece " phenomenon wherein occur, and anodal rate of finished products is 65%.
Comparative Examples 2
This Comparative Examples illustrates positive pole of prior art and preparation method thereof and comprises the lithium rechargeable battery that this is anodal.
Method according to embodiment 1 prepares positive pole and comprises the battery that this is anodal, and different is that the conductive agent of selecting for use is the carbon fiber for using among the embodiment 1 only.This Comparative Examples makes 108 of anodes altogether, defective just very 5 of " falling piece " phenomenon wherein occur, and anodal rate of finished products is 95.4%.
Embodiment 2-6
Embodiment illustrates positive pole provided by the invention and preparation method thereof and comprises the lithium rechargeable battery that this is anodal.
Anodal and comprise the battery that this is anodal according to the preparation of the method for embodiment 1, different is, conductive agent is as shown in table 1 below.
Table 1
Continuous table 1
As can be seen from Table 1, same adhesive and the hydrophily dispersant that contains hydrophilic adhesive that adopt, according to the present invention, it is 100: 1 to 100: 10 graphite and the carbon fiber embodiment as conductive agent that positive pole is selected weight ratio for use, anodal rate of finished products apparently higher than independent use acetylene black as the Comparative Examples 1 of conductive agent with use the Comparative Examples 2 of carbon fiber separately as conductive agent.
The test of battery multiplying power discharging:
To the battery that uses the foregoing description 1-6 and Comparative Examples 1-2 to make, carry out the test of battery multiplying power discharging respectively.Test environment is normal temperature, relative humidity 25-85%, and every kind of embodiment or Comparative Examples are measured 15 batteries respectively.Assay method is as follows:
Use BS-9300 (R) secondary cell device for detecting performance, electric current with 200 milliamperes (0.2C) charges to 3.8 volts to mesuring battary, shelved 5 minutes, be discharged to 3.0V in order to 1000 milliamperes (1C) then, shelved again 5 minutes, with 200 milliamperes of (0.2C) constant current charge to 4.2 volts, then with 4.2 volts of constant voltage charges, charging 20 milliamperes of cut-off currents (0.02C).The battery of substituting the bad for the good is discharged with 0.2C (200 milliamperes), 0.5C (500 milliamperes), 1C (1000 milliamperes) and 3C (3000 milliamperes) respectively, and discharging into cell voltage is 3.0 volts, the record discharge capacity.
Discharge capacity (milliampere-hour)=discharging current (milliampere) * discharge time (hour)
The discharge capacity of discharge capacity/0.2C of discharge-rate=0.5C or 1C or 3C * 100%
The results are shown in Table 2.
Table 2
From the result shown in the table 2 as can be seen, the battery multiplying power discharging property of embodiment illustrates that significantly better than Comparative Examples 1 and Comparative Examples 2 conductive agent of embodiment is evenly distributed, and conducts electricity very well.
Claims (11)
1. anode, this positive pole comprise collector and are coated in positive electrode on this collector; Described positive electrode comprises positive active material, conductive agent and adhesive, and described adhesive contains hydrophilic adhesive, it is characterized in that, described conductive agent comprises graphite and carbon fiber, and the weight ratio of described graphite and carbon fiber is 100: 1 to 100: 10.
2. anode according to claim 1, wherein, the weight ratio of described graphite and carbon fiber is 100: 2 to 100: 5.
3. anode according to claim 1 and 2, wherein, the median particle diameter D of described graphite
50Value is the 4-50 micron, and 002 interplanar distance that records with powder X-ray diffractometry is the 0.3354-0.3660 nanometer, and specific area is the 0.5-8 meters squared per gram.
4. anode according to claim 1 and 2, wherein, the length of described carbon fiber is the 10-100 micron, diameter is the 100-2000 nanometer.
5. according to the anode of claim 1, wherein, be benchmark with described positive electrode, the content of described conductive agent is 0.5-15 weight %, and the content of described adhesive is 0.01-8 weight %, and the content of described positive active material is 77-99 weight %; Described positive active material is selected from one or more in lithium cobalt oxygen, lithium nickel oxygen, lithium manganese oxygen, lithium-nickel-cobalt-oxygen, Li-Ni-Mn-O, lithium cobalt manganese oxygen and the Li-Ni-Mn-Co-O.
6. anode according to claim 1 or 5, wherein, described adhesive also contains hydrophobic adhesive, is benchmark with the adhesive, and the content of described hydrophilic adhesive is 25-100 weight %; Described hydrophilic adhesive is selected from one or more in hydroxypropyl methylcellulose, carboxymethyl cellulose, hydroxyethylcellulose and the polyvinyl alcohol; Described hydrophobic adhesive is selected from polytetrafluoroethylene and/or butadiene-styrene rubber.
7. the preparation method of the described anode of claim 1, this method comprises that the slurry that will contain positive electrode is coated on the collector, dry, calendering, described positive electrode comprises positive active material, conductive agent and adhesive, and described adhesive contains hydrophilic adhesive, it is characterized in that, described conductive agent comprises graphite and carbon fiber, and the weight ratio of described graphite and carbon fiber is 100: 1 to 100: 10.
8. method according to claim 7, wherein, the median particle diameter D of described graphite
50Value is the 4-50 micron, and 002 interplanar distance that records with powder X-ray diffractometry is the 0.3354-0.3660 nanometer, and specific area is the 0.5-8 meters squared per gram.
9. method according to claim 7, wherein, the length of described carbon fiber is the 10-100 micron, diameter is the 100-2000 nanometer.
10. method according to claim 7, wherein, the described slurry that contains positive electrode comprises positive electrode and dispersant, described dispersant is water and/or ethanol; With the described slurry that contains positive electrode is benchmark, and the content of described dispersant is 10-60 weight %.
11. a lithium rechargeable battery, this battery comprise battery container and are sealed in this battery container interior electrode group and electrolyte; Described electrode group comprises positive pole, negative pole and the barrier film between positive pole and negative pole, it is characterized in that, any described positive pole among the described just very claim 1-6.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2006101676750A CN101207189A (en) | 2006-12-21 | 2006-12-21 | Anode and preparation method thereof as well as lithium ion secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2006101676750A CN101207189A (en) | 2006-12-21 | 2006-12-21 | Anode and preparation method thereof as well as lithium ion secondary battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101207189A true CN101207189A (en) | 2008-06-25 |
Family
ID=39567185
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2006101676750A Pending CN101207189A (en) | 2006-12-21 | 2006-12-21 | Anode and preparation method thereof as well as lithium ion secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101207189A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102237526A (en) * | 2010-04-29 | 2011-11-09 | 上海比亚迪有限公司 | Lithium ion battery cathode slurry, cathode and battery |
| CN102237511A (en) * | 2010-04-22 | 2011-11-09 | 日立麦克赛尔能源株式会社 | Lithium secondary battery positive electrode and lithium secondary battery |
| CN102257658A (en) * | 2008-12-22 | 2011-11-23 | 住友化学株式会社 | Electrode mixture, electrode, and nonaqueous electrolyte secondary cell |
| CN102714297A (en) * | 2010-01-22 | 2012-10-03 | 丰田自动车株式会社 | Cathode and method for manufacturing the same |
| CN103177787A (en) * | 2011-12-26 | 2013-06-26 | 比亚迪股份有限公司 | Conductive powder used for preparing conductive silver paste and conductive silver paste |
| CN103531814A (en) * | 2013-10-28 | 2014-01-22 | 深圳格林德能源有限公司 | Composite conductive agent, dispersion method thereof, positive plate and lithium ion battery |
| CN108493400A (en) * | 2018-04-26 | 2018-09-04 | 广东永邦新能源股份有限公司 | A kind of high-voltage anode piece and preparation method thereof |
-
2006
- 2006-12-21 CN CNA2006101676750A patent/CN101207189A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102257658A (en) * | 2008-12-22 | 2011-11-23 | 住友化学株式会社 | Electrode mixture, electrode, and nonaqueous electrolyte secondary cell |
| CN102714297A (en) * | 2010-01-22 | 2012-10-03 | 丰田自动车株式会社 | Cathode and method for manufacturing the same |
| CN102237511A (en) * | 2010-04-22 | 2011-11-09 | 日立麦克赛尔能源株式会社 | Lithium secondary battery positive electrode and lithium secondary battery |
| CN105514358A (en) * | 2010-04-22 | 2016-04-20 | 日立麦克赛尔能源株式会社 | Method for manufacturing lithium secondary battery positive electrode and lithium secondary battery |
| CN102237526A (en) * | 2010-04-29 | 2011-11-09 | 上海比亚迪有限公司 | Lithium ion battery cathode slurry, cathode and battery |
| CN103177787A (en) * | 2011-12-26 | 2013-06-26 | 比亚迪股份有限公司 | Conductive powder used for preparing conductive silver paste and conductive silver paste |
| CN103177787B (en) * | 2011-12-26 | 2016-04-27 | 比亚迪股份有限公司 | A kind of conducting powder for the preparation of conductive silver paste and conductive silver paste |
| CN103531814A (en) * | 2013-10-28 | 2014-01-22 | 深圳格林德能源有限公司 | Composite conductive agent, dispersion method thereof, positive plate and lithium ion battery |
| CN108493400A (en) * | 2018-04-26 | 2018-09-04 | 广东永邦新能源股份有限公司 | A kind of high-voltage anode piece and preparation method thereof |
| CN108493400B (en) * | 2018-04-26 | 2020-07-24 | 广东永邦新能源股份有限公司 | High-voltage positive plate and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101207197B (en) | Lithium ion battery anode material and lithium ion battery and anode containing the material | |
| KR101966774B1 (en) | Negative electrode for secondary battery, preparation method thereof and secondary battery comprising the same | |
| CN100481609C (en) | A super capacitance cell | |
| CN101478042B (en) | Positive pole active substance, positive pole and battery | |
| CN101478041B (en) | Positive pole active substance, positive pole and battery | |
| US20070275302A1 (en) | Negative Electrode Material for Lithium Battery, and Lithium Battery | |
| CN109845005A (en) | Positive electrode active materials pre-dispersion composition, anode of secondary cell and the lithium secondary battery comprising the anode | |
| CN101212070A (en) | Laminated Li-ion secondary battery and method for producing the battery | |
| CN101207204A (en) | Lithium ion battery anode material and lithium ion battery and anode containing the material | |
| CN109659496A (en) | A kind of lithium ion cell positive film and its preparation and application | |
| CN102356490A (en) | Fluorinated binder composite materials and carbon nanotubes for positive electrodes for lithium batteries | |
| CN101154730A (en) | Lithium ion battery anode material and anode and lithium ion battery containing the said material | |
| CN101174682A (en) | Anode and method for producing the same and lithium ion secondary battery | |
| CN101207189A (en) | Anode and preparation method thereof as well as lithium ion secondary battery | |
| CN106602129A (en) | Multi-ion battery and preparation method thereof | |
| CN103891030A (en) | Nonaqueous electrolyte secondary battery and use of same | |
| CN103794814B (en) | A kind of lithium ion battery and preparation method thereof | |
| CN105308777A (en) | Negative electrode active material for electric device and electric device using same | |
| CN101453007B (en) | Negative electrode of lithium ionic secondary battery and battery thereof | |
| CN101453013A (en) | Negative electrode of lithium ionic cell, preparing method and cell thereof | |
| CN113540413A (en) | Positive electrode material, positive plate, lithium ion battery and preparation method thereof | |
| CN101315975A (en) | Battery anode and lithium ion battery using the same and their production method | |
| CN101414679A (en) | Composite material and preparation method thereof, and cathode and lithium battery | |
| CN101197436A (en) | Positive plate of lithium ion secondary battery, and battery including the same | |
| CN1971980A (en) | Anode of battery and lithium ion battery using the same and their preparation method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Open date: 20080625 |